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The DexNav is a feature in Omega Ruby and Alpha Sapphire that helps you easily find every Pokemon in the area, along with getting special abilities and eggmoves on almost any Pokemon. You get this feature very early ingame, right after you get the pokedex from professor Birch. If you look at your bottom screen, it is the red box with the magnifying glass and the Pikachu on it.

To find Luxio, you need to have beaten Kyogre/Groudon and stopped Team Magma/Team Aqua's evil plot. Professor Birch should tell you that lots of Pokemon native to other regions have arrived in Hoenn due to the temporary change in the climate. After that, you should be able to find Luxio in Route 118. To find it, you'll need to simply run around outside the grass and scare off any Pokemon that aren't Luxio until you hear it's cry. Then you sneak up on it and you should find one.

to extend on this answer: Luxio, along with many other pokemon are exclusive to this method, and you can't just run around in the grass to find these pokemon. Instead, you need wait for a pokemon to appear in the grass. This comes in the form of tails, glowing spots, dark lumps, and other shapes swaying in the grass. Sneak up on this spot using the left direction stick (not the D-pad) to start a battle. And as Shiny Hunter Luna stated, you can tell what the pokemon will be before you battle it by its cry